2646 J , Org. Chem., Vol. 41, No. 15,1976
Notes
H. J. Slater for expert technical assistance, and Drs. R. K. Blackwood and E. B. Whipple for stimulating discussions. Registry No.-la, 6342-56-9; lb, 5774-26-5; IC, 19358-00-0;1 4 59044-05-2;le, 19255-82-4;2a, 19358-03-3;2c, 59044-06-3;3a, 10374-97-7;3b, 38167-23-6;3c, 59044-07-4;4a, 59044-08-5;4b, 59043-78-6:4 ~ 59044-09-6: . 5. 59044-10-9:11. 59044-11-0:14. 59044-12-1; DHA,96-26-4; methanol, 67-56-1; ethanol, 64-17:5; 1: propanol, 71-23-8; isopropyl alcohol, 67-63-0; 1-butanol, 71-36-3; ethylene glycol, 107-21-1; 1,2-propanediol, 57-55-6; meso-2,3-butanediol, 5341-95-7; 1,3-propanediol, 504-63-2; glycerol, 56-81-5; 4ethoxy-5-methyl-3,6,8-trioxabicyclo[3.2.l]octane, 59044-13-2;4isopropoxy-5-methyl-3,6,8-trioxabicyclo[3.2.l]octane, 59044-14-3.
Novel One-Pot Synthesis of 4-Aminoquinazolines
References and Notes Part 4: S. K. Gupta, Synthesis, 726 (1975). R. W. Lemieux in "Molecular Rearrangements", Vol. 2, P. de Mayo, Ed., interscience, New York, N.Y., 1964, p 746. (a) M. Fedoronko and J. Konigstein, Collect. Czech. Chem. Commun., 34, 3881 (1969); (b) V. Prey, E. Waldmann, H. Berbalk, and F. Sommers, Monatsh. Chem., 85, 1186 (1954). V. R. Mattox, J. Am. Chem. Soc., 74,4340 (1952). R. M. Evans, G. F. H. Green, J. S. Hunt, A. G. Long, B. Mooney, and G. H. Phillips, J. Chem. Soc., 1529 (1958). S. Bernstein, M. Heller, and W. S. Allen, J. Org. Chem., 28, 1333 (1961). H. L. Herzog, M. J. Gentles, H. Marshall, and E. B. Hershberg, J. Am. Chem. Soc., 83, 4073 (1961). K. Tsuda, N. Ikekawa, and S. Nozoe, Chem. Pharm. Bull., 7, 519 (1959). E. Caspi, T. A. Wittstruck, and N. Grover, J. Org. Chem., 28, 763 (1963). The base-catalyzed reaction of DHA with o-erythrose gives mixed aldol reaction products: R. Schaffer, J. Org. Chem., 29, 1471 (1964). The acid.catalyzed derivatization of DHA has been reported: C. L. Bernier and W. L. Evans, J. Am. Chem. Soc., 60, 1381 (1938). E. Fuchs, Tetrahedron Lett., 1747 (1970), and references cited therein. (a) B. Fuchs, Y. Auerbach, and M. Sprecher, Tetrahedron, 30,437 (1974); (b) Y. Auerbach, M. Sprecher, and B. Fuchs, TetrahedronLett., 5207 (1970); (c)R. Bramley, L. A. Cort, and R. G. Pearson, J. Chem. SOC.C, 1213(1968); (d) C. Altona and E. Havinga, Tetrahedron, 2275 (1966). The formation of oxirane cations in the collisional activation mass spectra of 1,3-dioxolanes has recently been reported: C. C. Van de Sande and F. W. McLafferty, J. Am. Cbem. Soc., 97, 4613, 4617 (1975). For mass spectral data of analogous tetrathiadecalins and 1,3-dithiolanyl-l,3-dithiolanes, see D. L. Coffen, K. G. Bank, and P. E. Garrett, J. Org. Chem., 34, 605 (1969). M. Anteunis and F. Alderweireldt, Bull. SOC. Chim. Belg., 73, 889, 903 (1964). (15) For a recent discussion of the stereochemical analysis of 1,3dioxanes, see W. F. Bailey and E. L. Eliel, J. Am. Chem. SOC.,96, 1798 (1974); E. L. E M , J. R. Powers, Jr., and F. W. Nader, Tetrahedron, 30, 515 (1974); V. Usieli, A. Pilersdorf, S.Shor, J. Katzhendler, and S. Sarel, J. Org. Chem., 39, 2073 (1974); M. J. 0. Anteunis, D. Tavernier, and F. Bovvemans, Heterocycles, 4, 293 (1976). (16) Fluxional barriers in 4 may be considered analogous to the 9-methyl decalone system. For a discussion of the latter, see N. L. Allinger, G. A. Lane, and G. L. Wang, J. Org. Cbem., 39, 704 (1974), and references cited therein. (17) Structure 12 was eliminated on the basis of larger (0.1-0.2 ppm)anticipated shift for axial-equatorial oriented 4-CH3 substituent. Structure 13 should reveal only a single resonance for 4-CH3 group irrespective of the orientation of the methoxyl substituent. (18) For an alternate synthesis of trloxa-3,6,8-bicyclo[3.2.l]octanes, see J. Gelas, Bull. SOC.Chim. Fr., 3722, 4046 (1970). (19) The spectral data were obtained on the followin instruments: ir (PerklnElmer 337); 100-MHz 'H NMR (Varian A-60) and C NMR (Varian XL-100) and mass spectra (Perkin Elmer RMU-De). GLC analyses were performed on a Varian 2700 instrument equipped with a thermal conductivity detector using a 5 ft X 0.25 in., 5% FFAP on Fluoropak 80 column, He flow 60 mllmin. Fractional distillations were performed on a Nester-Faust Auto Annular Teflon spinning band unit Model TFA-200. Microanalyses were performed by Mr. T.Tooian and Miss A. McLellan of our Analytical Research Department. (20) Commercially available DHA (Wallerstein, Aldrich) was used in this study. DHA imparts tanning effect on skin. in addition to known monomeric and several dimeric forms,22 we have NMR (D20 solution) evidence for yet another possible dimer structure 14 for this compound. DHA (monomer) shows a singlet at 6 4.36 (D20).
B
H +- 4.1 (d, J
3.9 (d, J = 12 H d &
= 12 Hz)
c 3.51 (9)
3.68 (s)
/
